polypyrrole-magnetite dispersive micro-solid...

37
POLYPYRROLE-MAGNETITE DISPERSIVE MICRO-SOLID PHASE EXTRACTION FOR THE DETERMINATION OF RHODAMINE 6G AND CRYSTAL VIOLET IN TEXTILE WASTEWATER AMIRAH FARHAN BINTI KAMARUDDIN Universiti Teknologi Malaysia

Upload: dangcong

Post on 20-Mar-2019

221 views

Category:

Documents


0 download

TRANSCRIPT

POLYPYRROLE-MAGNETITE DISPERSIVE MICRO-SOLID PHASE

EXTRACTION FOR THE DETERMINATION OF RHODAMINE 6G AND

CRYSTAL VIOLET IN TEXTILE WASTEWATER

AMIRAH FARHAN BINTI KAMARUDDIN

Universiti Teknologi Malaysia

POLYPYRROLE-MAGNETITE DISPERSIVE MICRO-SOLID PHASE

EXTRACTION FOR THE DETERMINATION OF RHODAMINE 6G AND

CRYSTAL VIOLET IN TEXTILE WASTEWATER

AMIRAH FARHAN BINTI KAMARUDDIN

A dissertation submitted in partial fulfillment of the

requirements for the award of the degree of

Master of Science in Chemistry

Faculty of Science

Universiti Teknologi Malaysia

APRIL 2017

iii

To my beloved husband and mother

iv

ACKNOWLEDGEMENT

Alhamdulillah I have managed to complete this research. I am greatly indebted to

a number of people. First and foremost, I would like to express my deepest appreciation

to my supervisors, Dr. Aemi Syazwani Abdul Keyon and Prof. Dr. Mohd Marsin Sanagi

for their endless guidance throughout this research. Also, special thanks to my

colleagues who sincerely helped me regardless of the time. I am really thankful for their

priceless supervision and guidance, inspiring discussion and fruitful collaboration, all

their invaluable hours to provide constructive critics, enthusiasm and continuous

feedback. Without their continued support and patience, this dissertation would not have

been the same as presented here.

In preparing this valuable piece of work, I also received much excellent

encouragements, guidance and advices from Mr. Abdullah Ubaid Rahimi bin Che Mohd

Rahim, my beloved husband who gave me all the necessary support needed for success,

as such, I owe him a duty to be appreciative. This dissertation would not have been

possible without warm love of my family, who had always supported me in breathless

moments to happiness shelters despite of the distance. They showered me with love and

compassion and enrich my life like no other. Therefore, this work is dedicated to them.

I would like to thank all the laboratory assistants and staffs for their enlightening

companionship and encouragement of trudging through all the moments to complete this

dissertation. May ALLAH rewards all of you with His blessing.

v

ABSTRACT

Polypyrrole-magnetite (PPy-Fe3O4) dispersive micro-solid phase extraction

(PPy-Fe3O4-D-µ-SPE) method combined with ultraviolet-visible (UV-Vis)

spectrophotometry was developed for the determination of the selected basic dyes in

textile wastewater. PPy-Fe3O4 was used as adsorbent due to its stability and excellent

conductivity as well as capable of adsorbing the studied dyes. Two basic dyes,

Rhodamine 6G (Rh 6G) and Crystal Violet (CV) were chosen as model compounds.

Several important D-µ-SPE parameters were evaluated and optimized including sample

pH, amount of adsorbent, extraction time and type of desorption solvents. The optimum

PPy-Fe3O4-D-µ-SPE conditions were sample solution pH 8, 60 mg of PPy-Fe3O4

adsorbent, 5 min of extraction time and acetonitrile as the desorption solvent. Under the

optimized conditions, PPy-Fe3O4-D-µ-SPE method showed good linearity in the range

of 0.05-7 mg/L with coefficient of determination R2 > 0.998. The method showed good

limit of detection (LOD) for the basic dyes (0.05 mg/L) and good analyte recoveries

(97.4 to 111.3%) with relative standard deviations (RSD) < 10%. The developed method

was successfully applied to the analysis of real textile wastewater where the

concentration found was 1.03±7.9% mg/L and 1.13±4.6% mg/L for Rh 6G and CV

respectively. From the result, it can be concluded that PPy-Fe3O4-D-µ-SPE method can

be adopted for the extraction and analysis of trace level basic dyes in short time (total

analysis time < 15 min).

vi

ABSTRAK

Pengekstrakan fasa pepejal-mikro serakan ferum oksida bersalut polipirola (PPy-

Fe3O4-D-µ-SPE) bergandingan dengan ultraviolet (UV-Vis) spektrofotometri telah

dibangunkan bagi penentuan dua pewarna beralkali terpilih dalam air sisa tekstil. PPy-

Fe3O4 telah digunakan sebagai penjerap disebabkan kestabilannya, mempunyai

konduktiviti yang baik, luas permukaan yang tinggi dan juga mempunyai kebolehan

untuk menjerap pewarna yang dianalisis. Dua pewarna bes, rodamin 6G (Rh 6G) dan

kristal ungu (CV) telah dipilih sebagai sebatian model. Beberapa parameter yang penting

telah dinilai dan dioptimumkan termasuk sampel pH, amaun penjerap, masa

pengekstrakan dan jenis pelarut penyahjerapan. Keadaan optimum PPy-Fe3O4-D-µ-SPE

ialah pH 8, 60 mg penjerap PPy-Fe3O4, masa pengekstrakan selama 5 min dan asetonitril

sebagai pelarut penyahjerapan. Di bawah keadaan optimum, kaedah PPy-Fe3O4-D-µ-

SPE menunjukkan kelinearan yang baik dalam julat 0.05-7.00 mg/L dengan pekali

penentuan R2 > 0.998. Kaedah ini menunjukkan had pengesanan (LOD) yang baik untuk

pewarna beralkali yang dikaji (0.05 mg/L) dan pengembalian analit yang baik (97.4 to

111.3%) dengan sisihan piawai relative (RSD) < 10%. Kaedah yang dicadangkan telah

berjaya diaplikasikan pada analisis sampel air sisa tekstil yang sebenar di mana

kepekatan Rh 6G yang dikesan adalah 1.03±7.9% mg/L manakala CV mempunyai

1.13±4.6% mg/L. Dari hasil kajian ini, dapat dirumuskan bahawa kaedah PPy-Fe3O4-D-

µ-SPE boleh digunakan dalam pengekstrakan dan analisis pewarna beralkali pada tahap

yang rendah dalam masa yang singkat (jumlah masa analisis < 15 minit).

vii

TABLE OF CONTENTS

CHAPTER TITLE PAGE

DECLARATION ii

DEDICATION iii

ACKNOWLEDGEMENT iv

ABSTRACT v

ABSTRAK vi

TABLE OF CONTENTS vii

LIST OF TABLES x

LIST OF FIGURES xi

LIST OF ABBREVIATIONS xiii

1 INTRODUCTION

1.1 Background of Research 1

1.2 Problem Statement 5

1.3 Aim and Objectives of Research 6

1.4 Scope of Research 6

1.5 Significance of Study 7

viii

2 LITERATURE REVIEW

2.1 Organic-Inorganic Hybrid Materials 8

2.2 Polypyrrole-Magnetite Adsorbent 9

2.3 Dispersive Micro-Solid Phase Extraction 11

2.4 Basic Dyes 19

3 RESEARCH METHODOLOGY

3.1 Characterization of Polypyrrole and

Polypyrrole-Magnetite

23

3.2 Chemicals and Reagents 24

3.3 Apparatus and Instruments 25

3.4 UV Conditions for Analysis of Basic Dyes 25

3.5 Preparation of Standard Solutions 25

3.6 Study on Surface Charge of PPy-Fe3O4

Nanocomposite

26

3.7 D-µ-SPE of Dyes and Its Optimization Procedure 27

3.8 Method Validation 28

3.9 Preparation of Batik Textile Wastewater Sample 29

4 RESULTS AND DISCUSSION

4.1 Characterization of Polypyrrole-Magnetite,

PPy-Fe3O4

30

4.1.1 Fourier Transform Infrared Spectroscopy 30

4.1.2 Energy-Dispersive X-ray Spectroscopy 32

4.1.3 X-ray Diffraction Analysis 33

4.1.4 Nitrogen Adsorption Analysis 34

4.1.5 Field Emission Scanning Electron

Microscopy

34

4.1.6 Thermogravimetric Analysis 35

4.2 Surface Charge of PPy-Fe3O4 Nanocomposite 36

4.3 UV-Vis Determination and Standard Calibration

for Dyes

38

4.4 Optimization of D-µ-SPE Method 40

ix

4.4.1 Effect of Sample pH 40

4.4.2 Effect of Adsorbent Mass 41

4.4.3 Effect of Extraction Time 42

4.4.4 Effect of Desorption Solvents 43

4.5 Regeneration and Reusability Study of Adsorbent 44

4.6 Validation of D-µ-SPE Method 45

4.6.1 Linearity and Limit of Detection (LOD) 45

4.6.2 Precision and Accuracy 47

4.7 Application to Real Batik Textile Wastewater 48

5 CONCLUSION AND SUGGESTIONS

5.1 Conclusion 49

5.2 Suggestions 50

REFERENCES 51

x

LIST OF TABLES

TABLE NO. TITLE PAGE

2.1 Chemical structures and physicochemical

properties of studied dyes.

22

4.1 Percent composition of carbon, nitrogen, oxygen,

chlorine, iron in PPy-Fe3O4 nanocomposite by

EDAX analysis.

33

4.2 Analytical features of the D-µ-SPE coupled with

UV-Vis method for the analysis of basic dyes.

48

xi

LIST OF FIGURES

FIGURE NO. TITLE PAGE

3.1 Schematic diagram for the determination of

surface charge of PPy-Fe3O4 nanocomposite

26

3.2 Schematic diagram for D-µ-SPE optimization

procedure.

27

3.3 Schematic diagram for the preparation of batik

textile wastewater sample.

29

4.1 FTIR spectra of (a) original PPy and (b) PPy-

Fe3O4 nanocomposite.

31

4.2 EDAX spectrum of PPy-Fe3O4 nanocomposite. 32

4.3 XRD patterns of (a) original PPy and (b) PPy-

Fe3O4 nanocomposite.

33

4.4 FESEM image of (a) PPy and (b) PPy-Fe3O4

nanocomposite with average particle size

measurement of 90 nm.

35

4.5 TGA/DTA curves of (a) PPy and (b) PPy-

Fe3O4 nanocomposite.

36

xii

4.6 Determination of the pH of zero point of charge

(pHZPC) for PPy-Fe3O4 nanocomposite (40 mL

0.1 M NaNO3, 0.1 g PPy-Fe3O4 adsorbent,

stirring speed 220 rpm, ambient temperature).

37

4.7 UV-Vis spectra of the basic dyes. 38

4.8 Standard calibration graph of Rh 6G. 39

4.9 Standard calibration graph of CV. 39

4.10 Effect of sample pH. D-µ-SPE conditions:

adsorbent amount: 40 mg, extraction time: 2

min, desorption solvent: 500 µL methanol.

41

4.11 Effect of adsorbent amounts. D-µ-SPE

conditions: sample pH: pH 8, extraction time: 2

min, desorption solvent: 500 µL methanol.

42

4.12 Effect of extraction time. D-µ-SPE conditions:

sample pH: pH 8, adsorbent amount: 60 mg,

desorption solvent: 500 µL methanol.

43

4.13 Effect of desorption solvent. D-µ-SPE

conditions: sample pH: pH 8, adsorbent amount:

60 mg, extraction time: 5 min.

44

4.14 Method calibration curve for Rh 6G. D-µ-SPE

conditions: sample pH: pH 8, adsorbent amount:

60 mg, extraction time: 5 min, desorption

solvent: 500 µL of ACN. UV analysis at 527 nm.

46

4.15 Method calibration curve for CV. D-µ-SPE

conditions: sample pH: pH 8, adsorbent amount:

60 mg, extraction time: 5 min, desorption

solvent: 500 µL of ACN. UV analysis at 590 nm.

46

xiii

LIST OF ABBREVIATIONS

PAHs - Polycyclic aromatic hydrocarbons

PCBs - Polychlorinated biphenyls

OPPs - Organophosphorus pesticides

OCPs - Organochlorine pesticides

Rh 6G - Rhodamine 6G

CV - Crystal Violet

D-µ-SPE - Dispersive micro-solid phase extraction

PPy-Fe3O4 - Polypyrrole coated iron oxide

HPLC - High performance liquid chromatography

UV-Vis - Ultraviolet-visible

SPE - Solid phase extraction

FTIR - Fourier transform infrared

FESEM - Field emission scanning electron microscope

EDAX - Energy dispersive x-ray spectroscopy

XRD - x-ray diffraction

TGA - Thermogravimetric analysis

BET - Brunauer-Emmett-Teller

AC - Activated carbon

Fe3O4 - Magnetite

γ-Fe2O3 - Maghemite

PPy - Polypyrrole

xiv

LLE - Liquid-liquid extraction

µ-SPE - Micro-solid phase extraction

CNTs - Carbon nanotubes

Ag-SiO2-PDPA - silver nanoparticles-doped silica-polydiphenylamine

TiO2 - Titanium dioxide

MWCNTs-PVA - multiwalled carbon nanotubes/polyvinyl alcohol cryogel

composite

DEHP - di(2-ethylhexyl)phthalate

D-SPE - Dispersive solid phase extraction

CTAB - cetyltrimethylammonium bromide

zeolite NaY - sodium Y zeolite

NiZn:S - mixture of zinc acetate and nickel acetate with thioacetamide

MOF - metal-organic framework

MIL-101 - Material Institute Lavoisier 101

MNPs - Magnetic nanoparticles

HKUST - Hong Kong University of Science and Technology

EU - European Union

TAM - triarylmethane

C.I - Colour index

Mw - Molecular weight

log Kow - Octanol/water partition coefficient

N2 - Nitrogen gas

MeOH - Methanol

ACN - Acetonitrile

HEX - Hexane

NaNO3 - Sodium nitrate

NaOH - Sodium hydroxide

HNO3 - Nitric acid

pHZPC - pH of zero point of charge

HCl - Hydrochloric acid

xv

rpm - Revolution per minute

ppm - Parts per million

LOD - Limit of detection

RSD - Relative standard deviation

K - Kelvin

IUPAC - International Union of Pure and Applied Chemistry

R2 - Coefficient of determination

2

CHAPTER 1

INTRODUCTION

1.1 Background of Research

Environmental pollution has been a hot topic many years ago due to the

release of hazardous materials into environment. Furthermore, they exist beyond the

permitted limits. These hazardous materials are referring to environmental pollutants

or contaminants that can be any substances occurring naturally or man-made

including heavy metals (Li, Ma, van der Kuijp, Yuan, & Huang, 2014), polycyclic

aromatic hydrocarbons (PAHs) (Gavrilescu, Demnerova, Aamand, Agathos, & Fava,

2015), polychlorinated biphenyls (PCBs) (Gavrilescu et al., 2015; Noguera-Oviedo

& Aga, 2016), organophosphorus pesticides (OPPs), organochlorine pesticides

(OCPs), triazines herbicides (Noguera-Oviedo & Aga, 2016), phenolic compounds

(Deblonde, Cossu-Leguille, & Hartemann, 2011), triclosan (Dhillon, Kaur,

Pulicharla, Brar, Cledon, Verma, & Surampalli, 2015), textile dyes (Ashfaq &

Khatoon, 2014; Ribeiro & Umbuzeiro, 2014) and so on. Their presences are of

concern because they possess high toxicity and pose threat to public health even at

low concentration.

Therefore, the development of better analytical techniques always becomes

the top priority in any qualitative and quantitative research study. This is important in

order to study the properties of those pollutants such as physical state, oxidation

state, complexation form and others, as well as to extract and preconcentrate them at

trace level. Besides, monitoring activities for these contaminants in different food

and environmental samples such as soil, air and water can also be done in order to

2

avoid long term exposure. However, it is not easy to analyze unknown or known

species at trace levels especially in complex environmental matrices.

Textile industry, for example in the process of batik painting, requires a large

quantity of dyes and other chemicals, as well as large volume of water for washing.

The problem lies when this industry discharges wastewater containing harmful dyes

into the environment without appropriate treatment. This discharge of dyes has posed

difficulty to be decolorized and decomposed biologically due to their resistant

against the light exposure, water and many chemicals. The dyes in wastewater can

increase not only environmental degradation like depletion of dissolved oxygen

needed by marine life, loss of soil productivity, but also risks human illness for

example the bad quality of drinking water for human consumption.

As this industry generates effluents containing large quantity of dyes into the

environment, the waste is considered as pollutants due to their threats to public as

such they consist of carcinogens like benzidine (Padhi, 2012). In addition, they have

large variety of functional groups which contribute to their diverse properties. That is

the reason the detection of these dyes becomes a major wastewater challenge. The

highly undesirable presence of dyes at low concentration in wastewater is indeed a

concern due to their toxicity, carcinogenic, and other harmful effects either to aquatic

life or even human health for example bladder cancer in humans (Padhi, 2012).

The maximum concentration of dyes in water of more than 1 mg/L caused by

untreated textile effluents can harm the public health (Carmen & Daniela, 2012). In

addition, high concentrations of textile dyes in water bodies can prevent the re-

oxygenation capacity of the receiving water and cut-off sunlight. Consequently, it

would affect the biological activity in aquatic life and also the photosynthesis process

of aquatic plants or algae (Carmen & Daniela, 2012). The targeted dyes to be

analyzed are Rhodamine 6G (Rh 6G) and Crystal Violet (CV) because they are the

commonly used basic dyes in the textile batik industry. Furthermore, they are readily

available in the laboratory and not costly. Therefore, it is imperative to develop much

simpler and low cost techniques. This technique is important not only due to its

4

economical aspect but can also improve the quality of drinking water resources that

have been contaminated with pathogens originating from wastewater.

During past decades, many conventional methods have been reported in dye

analysis, yet they are high in cost and often less adaptable in wastewater containing

dyes. A simple and economical technique known as dispersive micro-solid phase

extraction (D-µ-SPE) is developed in this new application of dye analysis. Not only

it is easy to operate, it is also effective as such the mode of its mechanism is an

adsorption process. Importantly, since D-µ-SPE method requires the use of

adsorbent, the economic aspect of the whole procedure including the search of less

costly adsorbent material becomes the top priority especially in wastewater

treatment.

Adsorption is known as an economical, effective and simple method to

extract targeted species from aqueous matrix (Gupta, Ali, Saleh, Nayaka, & Agarwal,

2012) and commonly applicable in industry and laboratories for green extraction

purposes. Many kinds of adsorbents have been developed for example natural

materials like agro-waste products (Gupta & Suhas, 2009; Tran, Ngo, Guo, Zhang,

Liang, Ton-That, & Zhang, 2015), clay (Srinivasan, 2011; Gupta & Suhas, 2009),

biopolymer (Sanagi, Loh, Wan Ibrahim, Pourmand, Salisu, Ali, 2016; Tran et al.,

2015), zeolite (Delkash, Bakhshayesh, & Kazemian, 2015), ion exchange resin

(Bilal, Shah, Ashfaq, Gardazi, Tahir, Pervez, & Mahmood, 2013; Nagarale, Gohil, &

Shahi, 2006), activated carbons (Sharma, Kaur, Sharma, & Sahore, 2011) and many

more. Agro-waste products, clays and biopolymers are environmental friendly and

can be found in large amount. However, they had low adsorption capacity (Sharma

et al., 2011; Yang & Han, 2005) and insufficient stability data in real wastewater

sample (Tran et al., 2015). As a result, some modification steps are required to

overcome their drawbacks but still, the production cost is high depending on the

modification conditions.

3

4

Zeolites, they have two kinds of them which are natural and synthetic

zeolites. Natural zeolites can also be found in abundance and inexpensive price, but

they had capability to degrade the water quality when they have low content of

zeolite. They should not contain any water-soluble impurities in order to prevent

contamination of water sample (Delkash et al., 2015). For synthetic zeolites, they are

more expensive than the natural one but they have high efficiency and high cation

exchange capacity. The recovery, enrichment as well as the removal of ionic

pollutants can be performed by ion exchange resins but the problem with these

adsorbents is when there is a change in concentration of ionic solutions, they have

low selectivity, low mechanical stability and high degree of swellness or shrinkage

(Nagarale et al., 2006). Activated carbon which is a commonly used adsorbent due to

its efficiency and applicable to wide range of analyte adsorption, its usage could still

be restricted due to economical consideration, poor regeneration ability and

generation of large amount of greenhouse gases during its production stage (Shankar,

2008; Gupta & Suhas, 2009).

The main highlight of this study is the use of synthetic organic-inorganic

hybrid based nanomaterials; polypyrrole-magnetite (PPy-Fe3O4) as adsorbent for the

adsorption and desorption of textile dyes. The organic-inorganic hybrid-based

adsorbent has gained attention in many separation studies for instance as adsorbents

for water treatment purpose (Samiey, Cheng, & Wu, 2014), packing materials in high

performance liquid chromatography (HPLC) column (Xiong, Yang, Huang, Jiang,

Chen, Shen, & Chen, 2013) and others (Souza & Quadri, 2013). These are all

because of their high selectivity, permeability, mechanical and chemical stability

(Kango, Kalia, Celli, Njuguna, Habibie, & Kumara, 2013). They are also very

flexible to adjust their structure and properties depending on the synthesis process

and conditions they possess. Ultraviolet-visible (UV-Vis) spectrophotometer is a

commonly used detection technique in dyes analysis and mostly available in most

laboratories, thus, it is used in the current study.

4

1.2 Problem Statement

In Southeast Asia, textile industry especially batik production is very famous

and the generation of dye wastewater indeed becomes a concern. This untreated

wastewater can cause cancer and abnormalities (Koay, Ahamad, Nourouzi, Abdullah,

& Choong, 2013). Furthermore, in Malaysia, a 2013 year statistic showed that the

percentage of clean rivers was reduced by 1 % (Manan, Chai, & Samad, 2015).

Likewise, there had been also a case in United States where the government had to

spent around USD 76.6 billion to treat the children affected by this environmentally

mediated diseases like prenatal methylmercury exposure, lead poisoning, childhood

cancer, intellectual disability and other related diseases (Trasande & Liu, 2011). It

showed that the emergence of these environmental pollutants is indeed harmful

towards public health especially young generation by slowing down the development

and learning ability of an individual. Besides, these water and air pollution problems

can also lead to death (Prüss-Üstün, Bonjour, & Corvalán, 2008). Many conventional

treatments had been done to treat wastewater for example oxidation, photo-

degradation process and ozonation (Hozhabr Araghi & Entezari, 2015) but these

methods have shortcomings of producing more toxic intermediates compared to the

original compound. Adsorbents like agro-waste products, clays and biopolymers,

they are environmentally friendly but they had low adsorption capacity and unstable

in real wastewater samples. Therefore, advances in the analysis of wastewater make

it possible to detect the dyes present in textile wastewater by employing adsorption

process of newly developed solid phase extraction (SPE) technique termed D-µ-SPE.

As D-µ-SPE method being developed with the introduction of better performance

adsorbents, magnetic nanoparticles come in the interest of researchers due to their

high surface area and easy separation from aqueous media using external magnet.

The combination of organic and inorganic materials termed organic-inorganic

hybrid-based nanocomposite is introduced as the studied adsorbent together with D-

µ-SPE method as the heart of this study.

5

4

1.3 Aim and Objectives of Research

The aim of this study is to develop an improved microextraction method

using organic-inorganic hybrid-based adsorbent for the determination of basic

dyes from water sample. In order to achieve the aim, several objectives are

proposed to:

i. Characterize previously prepared in-house polypyrrole-magnetite

(PPy-Fe3O4) nanocomposite.

ii. Utilize the material as adsorbent in dispersive micro-solid phase

extraction (D-µ-SPE) method for the extraction of Rhodamine 6G (Rh

6G) and Crystal Violet (CV) dyes.

iii. Optimize and validate the D-µ-SPE method for the analysis of dyes in

water.

iv. Apply the developed D-µ-SPE method to the analysis of dyes in real

wastewater sample from batik textile industry.

1.4 Scope of Research

This research focuses on the characterization of a new composite material,

PPy-Fe3O4 to be utilized as adsorbent in D-µ-SPE method. For this study, in-house

synthesized material (PPy-Fe3O4) is used as an adsorbent for the extraction of Rh 6G

and CV. PPy-Fe3O4 nanocomposite is characterized using Fourier Transform Infrared

(FTIR) spectroscopy, field emission scanning electron microscope (FESEM),

energy-dispersive X-ray spectroscopy (EDAX), X-ray diffraction (XRD),

thermogravimetric analysis (TGA) and nitrogen adsorption analysis (BET), and its

performance as D-µ-SPE adsorbent is investigated.

6

4

This study then focuses on the optimized D-µ-SPE procedure required where

the parameters involved are sample pH, adsorbent mass, extraction time and type of

desorption solvents. The analysis is carried out using UV-Vis spectrophotometer. It

involves the mechanism of adsorption process as it is a suitable treatment option for

organic contaminants (Pirkarami & Olya, 2014). The optimized and validated

methods are then applied to analyze the targeted dyes in real wastewater sample from

a batik factory in Kota Bharu, Kelantan.

1.5 Significance of Study

This study is very important to study the capabilities of the newly applied

adsorbent in the extraction of the basic dyes in wastewater prior to their

determination by UV-Vis spectrophotometer instrument. The adsorbent studied is

thermally stable and can be reusable generally while the extraction technique used is

environmentally friendly, faster and efficient. In addition, it is also expected that the

developed low-cost and efficient technique will be a useful tool for the

preconcentration of other analytes in various water samples.

7

REFERENCES

Appusamy, A., John, I., Ponnusamy, K., & Ramalingam, A. (2014). Removal of

crystal violet dye from aqueous solution using triton X-114 surfactant via

cloud point extraction. Engineering Science and Technology, an International

Journal, 17(3), 137-144.

Asgharinezhad, A. A., Ebrahimzadeh, H., Mirbabaei, F., Mollazadeh, N., & Shekari,

N. (2014). Dispersive micro-solid-phase extraction of benzodiazepines from

biological fluids based on polyaniline/magnetic nanoparticles composite.

Analytica Chimica Acta, 844, 80-89.

Asgharinezhad, A. A., Mollazadeh, N., Ebrahimzadeh, H., Mirbabaei, F., & Shekari,

N. (2014). Magnetic nanoparticles based dispersive micro-solid-phase

extraction as a novel technique for coextraction of acidic and basic drugs

from biological fluids and waste water. Journal of Chromatography A, 1338,

1-8.

Ashfaq, A., & Khatoon, A. (2014). Waste management of textiles: A solution to the

environmental pollution. International Journal of Current Microbiology and

Applied Science, 3(7), 780-787.

Bafana, A., Devi, S. S., & Chakrabarti, T. (2011). Azo dyes: past, present and the

future. Environmental Reviews, 19(NA), 350-371.

Bagheri, H., & Banihashemi, S. (2015). Sol–gel-based silver nanoparticles-doped

silica – Polydiphenylamine nanocomposite for micro-solid-phase extraction.

Analytica Chimica Acta, 886, 56-65.

52

Baig, U., Rao, R. A. K., Khan, A. A., Sanagi, M. M., & Gondal, M. A. (2015).

Removal of carcinogenic hexavalent chromium from aqueous solutions using

newly synthesized and characterized polypyrrole–titanium(IV)phosphate

nanocomposite. Chemical Engineering Journal, 280, 494-504.

Ballarin, B., Mignani, A., Mogavero, F., Gabbanini, S., & Morigi, M. (2015). Hybrid

material based on ZnAl hydrotalcite and silver nanoparticles for deodorant

formulation. Applied Clay Science, 114, 303-308.

Basheer, C., Chong, H. G., Hii, T. M., & Lee, H. K. (2007). Application of Porous

Membrane-Protected Micro-Solid-Phase Extraction Combined with HPLC

for the Analysis of Acidic Drugs in Wastewater. Analytical Chemistry,

79(17), 6845-6850.

Basheer, C., Narasimhan, K., Yin, M., Zhao, C., Choolani, M., & Lee, H. K. (2008).

Application of micro-solid-phase extraction for the determination of

persistent organic pollutants in tissue samples. Journal of Chromatography A,

1186(1–2), 358-364.

Bilal, M., Shah, J.A., Ashfaq, T., Gardazi, S.M.H., Tahir, A.A., Pervez, A., &

Mahmood, Q. (2013). Waste biomass adsorbents for copper removal from

industrial wastewater - A review. Journal of Hazardous Materials, 263, 322-

333.

Cao, W., Hu, S. S., Ye, L. H., & Cao, J. (2014). Dispersive micro-solid-phase

extraction using mesoporous hybrid materials for simultaneous determination

of semivolatile compounds from plant tea by ultra-high-performance liquid

chromatography coupled with quadrupole time-of-flight tandem mass

spectrometry. Journal of Agricultural and Food Chemistry, 62(40), 9683-

9689.

53

Carmen, Z., & Daniela, S. (2012). Textile organic dyes–characteristics, polluting

effects and separation/elimination procedures from industrial effluents–a

critical overview. Paper presented at the Organic Pollutants Ten Years After

the Stockholm Convention-Environmental and Analytical Update.

Carneiro, P. A., Nogueira, R. F. P., & Zanoni, M. V. B. (2007). Homogeneous

photodegradation of CI Reactive Blue 4 using a photo-Fenton process under

artificial and solar irradiation. Dyes and Pigments, 74(1), 127-132.

Chang, Y. P., Ren, C. L., Yang, Q., Zhang, Z. Y., Dong, L. J., Chen, X. G., & Xue,

D. S. (2011). Preparation and characterization of hexadecyl functionalized

magnetic silica nanoparticles and its application in Rhodamine 6G removal.

Applied Surface Science, 257(20), 8610-8616.

Chen, D., Miao, H., Zou, J., Cao, P., Ma, N., Zhao, Y., & Wu, Y. (2015). Novel

dispersive micro-solid-phase extraction combined with ultrahigh-performance

liquid chromatography–high-resolution mass spectrometry to determine

morpholine residues in citrus and apples. Journal of Agricultural and Food

Chemistry, 63(2), 485-492.

Dalali, N., Khoramnezhad, M., Habibizadeh, M., & Faraji, M. (2011). Magnetic

removal of acidic dyes from waste waters using surfactant-coated magnetite

nanoparticles: optimization of process by Taguchi method. Paper presented at

the International conference on environmental and agriculture engineering

IPCBEE, Singapore.

Deblonde, T., Cossu-Leguille, C., & Hartemann, P. (2011). Emerging pollutants in

wastewater: a review of the literature. Int J Hyg Environ Health, 214(6), 442-

448.

Delkash, M., Bakhshayesh, B.E., & Kazemian, H. (2015). Using zeolitic adsorbents

to cleanup special wastewater streams: A review. Microporous Mesoporous

Materials, 214, 224-241.

54

Dhillon, G. S., Kaur, S., Pulicharla, R., Brar, S. K., Cledón, M., Verma, M., &

Surampalli, R. Y. (2015). Triclosan: Current Status, Occurrence,

Environmental Risks and Bioaccumulation Potential. International Journal of

Environmental Research and Public Health, 12(5), 5657-5684.

Din, M. I., Ata, S., Mohsin, I. U., Rasool, A., & Andleeb Aziz, A. (2014). Evaluation

of conductive polymers as an adsorbent for eradication of As (III) from

aqueous solution using inductively coupled plasma optical emission

spectroscopy (ICP-OES) (Vol. 6).

Farhadi, K., Matin, A. A., Amanzadeh, H., Biparva, P., Tajik, H., Farshid, A. A., &

Pirkharrati, H. (2014). A novel dispersive micro solid phase extraction using

zein nanoparticles as the sorbent combined with headspace solid phase micro-

extraction to determine chlorophenols in water and honey samples by GC–

ECD. Talanta, 128, 493-499.

Freire, M. G. (2016). Ionic-Liquid-Based Aqueous Biphasic Systems: Fundamentals

and Applications: Springer Berlin Heidelberg.

Fu, S. C., Tzing, S. H., Chen, H. C., Wang, Y. C., & Ding, W. H. (2012). Dispersive

micro-solid phase extraction combined with gas chromatography-chemical

ionization mass spectrometry for the determination of N-nitrosamines in

swimming pool water samples. Analytical and Bioanalytical Chemistry,

402(6), 2209-2216.

Gavrilescu, M., Demnerova, K., Aamand, J., Agathos, S., & Fava, F. (2015).

Emerging pollutants in the environment: present and future challenges in

biomonitoring, ecological risks and bioremediation. New Biotechnology,

32(1), 147-156.

55

González-Fuenzalida, R. A., Moliner-Martinez, Y., Verdú-Andrés, J., Molins-Legua,

C., Herráez-Hernández, R., Jornet-Martinez, N., & Campíns-Falcó, P. (2015).

Microextraction with phases containing nanoparticles. Bioanalysis, 7(17),

2163-2170.

Gu, Z.-Y., Yang, C.-X., Chang, N., & Yan, X.-P. (2012). Metal–organic frameworks

for analytical chemistry: from sample collection to chromatographic

separation. Accounts of Chemical Research, 45(5), 734-745.

Guo, J., Gu, H., Wei, H., Zhang, Q., Haldolaarachchige, N., Li, Y., & Guo, Z.

(2013). Magnetite–polypyrrole metacomposites: Dielectric properties and

magnetoresistance behavior. The Journal of Physical Chemistry C, 117(19),

10191-10202.

Gupta, V.K., Ali, I., Saleh, T.A., Nayaka, A., & Agarwal, S. (2012). Chemical

treatment technologies for wastewater recycling - An overview. ACS

Advances, 2, 6380-6388.

Gupta, V.S., & Suhas. (2009). Application of low-cost adsorbents for dye removal -

A review. Journal of Environmental Management, 90, 2313-2342.

Han, S. I., Han, K. H., Frazier, A. B., Ferrance, J. P., & Landers, J. P. (2009). An

automated micro-solid phase extraction device involving integrated high-

pressure microvalves for genetic sample preparation. Biomedical

Microdevices, 11(4), 935-942.

Hasan, Z., Jeon, J., & Jhung, S. H. (2012). Adsorptive removal of naproxen and

clofibric acid from water using metal-organic frameworks. Journal of

Hazardous Materials, 209, 151-157.

Hettige, A., & Mowjood, M. (2015). Reduction of colour in treated wastewater from

textile industry using sawdusts as bio-sorbents. Tropical Agricultural

Research, 26(4).

56

Hozhabr Araghi, S., & Entezari, M. H. (2015). Amino-functionalized silica

magnetite nanoparticles for the simultaneous removal of pollutants from

aqueous solution. Applied Surface Science, 333, 68-77.

Hu, Y., Song, C., Liao, J., Huang, Z., & Li, G. (2013). Water stable metal-organic

framework packed microcolumn for online sorptive extraction and direct

analysis of naproxen and its metabolite from urine sample. Journal of

Chromatography A, 1294, 17-24.

Huo, K., Gao, B., Fu, J., Zhao, L., & Chu, P. K. (2014). Fabrication, modification,

and biomedical applications of anodized TiO2 nanotube arrays. RSC

Advances, 4(33), 17300-17324.

Jain, R., Mathur, M., Sikarwar, S., & Mittal, A. (2007). Removal of the hazardous

dye rhodamine B through photocatalytic and adsorption treatments. Journal

of Environmental Management, 85(4), 956-964.

Jiao, Z., Zhu, D., & Yao, W. (2015). Combination of accelerated solvent extraction

and micro-solid-phase extraction for determination of trace antibiotics in food

samples. Food Analytical Methods, 8(9), 2163-2168.

Jiménez-Soto, J. M., Cárdenas, S., & Valcárcel, M. (2012). Dispersive micro solid-

phase extraction of triazines from waters using oxidized single-walled carbon

nanohorns as sorbent. Journal of Chromatography A, 1245, 17-23.

Jin, X., Li, Y., Yu, C., Ma, Y., Yang, L., & Hu, H. (2011). Synthesis of novel

inorganic–organic hybrid materials for simultaneous adsorption of metal ions

and organic molecules in aqueous solution. Journal of Hazardous Materials,

198, 247-256.

Judeinstein, P., & Sanchez, C. (1996). Hybrid organic-inorganic materials: A land of

multidisciplinary. Journal of Material Chemistry, 6, 511-525.

56

57

Kango, S., Kalia, S., Celli, A., Njuguna, J., Habibie, Y., & Kumara, R. (2013).

Surface modification of inorganic nanoparticles for development of organic-

inorganic nanocomposites - A review. Progress in Polymer Science, 38,

1232-1261.

Kanimozhi, S., Basheer, C., Narasimhan, K., Liu, L., Koh, S., Xue, F., & Lee, H. K.

(2011). Application of porous membrane protected micro-solid-phase-

extraction combined with gas chromatography–mass spectrometry for the

determination of estrogens in ovarian cyst fluid samples. Analytica Chimica

Acta, 687(1), 56-60.

Kanta, A. F., Poelman, M., & Decroly, A. (2015). Electrochemical characterisation

of TiO2 nanotube array photoanodes for dye-sensitized solar cell application.

Solar Energy Materials and Solar Cells, 133, 76-81.

Kar, P., Farsinezhad, S., Mahdi, N., Zhang, Y., Obuekwe, U., Sharma, H., &.

Shankar, K. (2016). Enhanced CH4 yield by photocatalytic CO2 reduction

using TiO2 nanotube arrays grafted with Au, Ru, and ZnPd nanoparticles.

Nano Research, 9(11), 3478-3493.

Karthik, S., Gopal, K. M., Haripriya, E. P., Sorachon, Y., Maggie, P., Oomman, K.

V., & Craig, A. G. (2007). Highly-ordered TiO2 nanotube arrays up to

220 µm in length: Use in water photoelectrolysis and dye-sensitized solar

cells. Nanotechnology, 18(6), 065707.

Khayoon, W. S., Saad, B., Salleh, B., Manaf, N. H. A., & Latiff, A. A. (2014).

Micro-solid phase extraction with liquid chromatography–tandem mass

spectrometry for the determination of aflatoxins in coffee and malt beverage.

Food Chemistry, 147, 287-294.

58

Khodadoust, S., Talebianpoor, M. S., & Ghaedi, M. (2014). Application of an

optimized dispersive nanomaterial ultrasound‐assisted microextraction

method for preconcentration of carbofuran and propoxur and their

determination by high‐performance liquid chromatography with UV

detection. Journal of Separation Science, 37(21), 3117-3124.

Koay, Y. S., Ahamad, I. S., Nourouzi, M. M., Abdullah, L. C., & Choong, T. S. Y.

(2013). Development of Novel Low-Cost Quaternized Adsorbent from Palm

Oil Agriculture Waste for Reactive Dye Removal (Vol. 9).

Kueseng, P., Thammakhet, C., Thavarungkul, P., & Kanatharana, P. (2010).

Multiwalled carbon nanotubes/cryogel composite, a new sorbent for

determination of trace polycyclic aromatic hydrocarbons. Microchemical

Journal, 96(2), 317-323.

Li, J., Wang, Y. B., Li, K. Y., Cao, Y. Q., Wu, S., & Wu, L. (2015). Advances in

different configurations of solid-phase microextraction and their applications

in food and environmental analysis. TrAC Trends in Analytical Chemistry,

72, 141-152.

Li, N., Zhang, L., Nian, L., Cao, B., Wang, Z., Lei, L., & Yu, A. (2015). Dispersive

micro-solid-phase extraction of herbicides in vegetable oil with metal–

organic framework MIL-101. Journal of Agricultural and Food Chemistry,

63(8), 2154-2161.

Li, Z., Ma, Z., van der Kuijp, T. J., Yuan, Z., & Huang, L. (2014). A review of soil

heavy metal pollution from mines in China: Pollution and health risk

assessment. Science of The Total Environment, 468–469, 843-853.

Lopez, J. A., González, F., Bonilla, F. A., Zambrano, G., & Gómez, M. E. (2010).

Synthesis and characterization of Fe3O4 magnetic nanofluid. Revista

Latinoamericana de Metalurgia y Materiales, 60-66.

59

Mahmoud, M. E., Hafez, O. F., Alrefaay, A., & Osman, M. M. (2010). Performance

evaluation of hybrid inorganic/organic adsorbents in removal and

preconcentration of heavy metals from drinking and industrial waste water.

Desalination, 253(1–3), 9-15.

Mahmoud, M. E., Hafez, O. F., Osman, M. M., Yakout, A. A., & Alrefaay, A.

(2010). Hybrid inorganic/organic alumina adsorbents-functionalized-

purpurogallin for removal and preconcentration of Cr(III), Fe(III), Cu(II),

Cd(II) and Pb(II) from underground water. Journal of Hazardous Materials,

176(1–3), 906-912.

Mahmoudian, M., Alias, Y., Basirun, W., Woi, P. M., Baradaran, S., & Sookhakian,

M. (2014). Synthesis, characterization, and sensing applications of

polypyrrole coated Fe3O4 nanostrip bundles. Ceramics International, 40(7),

9265-9272.

Mahpishanian, S., & Sereshti, H. (2014). Graphene oxide-based dispersive micro-

solid phase extraction for separation and preconcentration of nicotine from

biological and environmental water samples followed by gas

chromatography-flame ionization detection. Talanta, 130, 71-77.

Makkliang, F., Kanatharana, P., Thavarungkul, P., & Thammakhet, C. (2015).

Development of magnetic micro-solid phase extraction for analysis of

phthalate esters in packaged food. Food Chemistry, 166, 275-282.

Manan, F. A., Chai, T. T., & Samad, A. A. (2015). Environmental pollution in

Malaysia: Are medicinal plants potential phytoremediation agents? Maejo

International Journal of Science and Technology, 9(3), 288.

Muliwa, A. M., Leswifi, T. Y., Onyango, M. S., & Maity, A. (2016). Magnetic

adsorption separation (MAS) process: An alternative method of extracting

Cr(VI) from aqueous solution using polypyrrole coated Fe3O4

nanocomposites. Separation and Purification Technology, 158, 250-258.

60

Naeemullah, Kazi, T. G., Afridi, H. I., Shah, F., Arain, S. S., Arain, S. A., &

Samoon, M. K. (2016). Development of new portable miniaturize solid phase

microextraction of silver-APDC complex using micropipette tip in-syringe

system couple with electrothermal atomic absorption spectrometry.

Spectrochimica Acta Part A: Molecular Biomolecular Spectroscopy, 154,

157-163.

Nagarale, R.K., Gohil, G.S., & Shahi, V.K. (2006). Recent developments on ion-

exchange membranes and electro-membrane processes. Advances in Colloid

and Interface Science, 119, 97-130.

Noguera-Oviedo, K., & Aga, D. S. (2016). Lessons learned from more than two

decades of research on emerging contaminants in the environment. Journal of

Hazardous Materials, 316, 242-251.

Ogugbue, C. J., & Sawidis, T. (2011). Bioremediation and detoxification of synthetic

wastewater containing triarylmethane dyes by aeromonas hydrophila isolated

from industrial effluent. Biotechnology Research International, 2011, 11.

Othman, N., Yi, O. Z., Zailani, S. N., Zulkifli, E. Z., & Subramaniam, S. (2013).

Extraction of rhodamine 6g dye from liquid waste solution: study on

emulsion liquid membrane stability performance and recovery. Separation

Science and Technology, 48(8), 1177-1183.

Padhi, B. (2012). Pollution due to synthetic dyes toxicity & carcinogenicity studies

and remediation. International Journal of Environmental Sciences, 3(3), 940.

Pal, U., Sandoval, A., Madrid, S. I. U., Corro, G., Sharma, V., & Mohanty, P. (2016).

Mixed titanium, silicon, and aluminum oxide nanostructures as novel

adsorbent for removal of rhodamine 6G and methylene blue as cationic dyes

from aqueous solution. Chemosphere, 163, 142-152.

61

Pan, B., Pan, B., Zhang, W., Lv, L., Zhang, Q., & Zheng, S. (2009). Development of

polymeric and polymer-based hybrid adsorbents for pollutants removal from

waters. Chemical Engineering Journal, 151(1–3), 19-29.

Pereira, L., & Alves, M. (2012). Dyes-environmental impact and remediation

Environmental protection strategies for sustainable development (pp. 111-

162): Springer.

Pirkarami, A., & Olya, M. E. (2014). Removal of dye from industrial wastewater

with an emphasis on improving economic efficiency and degradation

mechanism. Journal of Saudi Chemical Society, 21, 179-186.

Pruss-Ustun, A., Bonjour, S., & Corvalan, C. (2008). The impact of the environment

on health by country: A meta-synthesis. Environmental Health, 7,7.

Qi, F., Qian, L., Liu, J., Li, X., Lu, L., & Xu, Q. (2016). A high-throughput

nanofibers mat-based micro-solid phase extraction for the determination of

cationic dyes in wastewater. Journal of Chromatography A, 1460, 24-32.

Rai, A. K., Das, I. M. L., Uttam, K. N., & Department, U. o. A. P. (2010). Emerging

Trends in Laser & Spectroscopy and Applications: Allied Publishers Pvt.

Limited.

Ramesan, M. T. (2013). Preparation and properties of

Fe3O4/polypyrrole/poly(pyrrole-co-acrylamide) nanocomposites.

International Journal of Polymeric Materials and Polymeric Biomaterials,

62(5), 277-283.

Ribeiro, A. R., & Umbuzeiro, G. d. A. (2014). Effects of a textile azo dye on

mortality, regeneration, and reproductive performance of the planarian,

Girardia tigrina. Environmental Sciences Europe, 26(1), 22.

62

Rocío-Bautista, P., Martínez-Benito, C., Pino, V., Pasán, J., Ayala, J. H., Ruiz-Pérez,

C., & Afonso, A. M. (2015). The metal–organic framework HKUST-1 as

efficient sorbent in a vortex-assisted dispersive micro solid-phase extraction

of parabens from environmental waters, cosmetic creams, and human urine.

Talanta, 139, 13-20.

Rocío-Bautista, P., Pino, V., Ayala, J. H., Pasán, J., Ruiz-Pérez, C., & Afonso, A. M.

(2016). A magnetic-based dispersive micro-solid-phase extraction method

using the metal-organic framework HKUST-1 and ultra-high-performance

liquid chromatography with fluorescence detection for determining

polycyclic aromatic hydrocarbons in waters and fruit tea infusions. Journal of

Chromatography A, 1436, 42-50.

Sabnis, R. W. (2007). Handbook of Acid-Base Indicators: CRC Press.

Sadegh, H., Shahryari-Ghoshekandi, R., Masjedi, A., Mahmoodi, Z., & Kazemi, M.

(2016). A review on carbon nanotubes adsorbents for the removal of

pollutants from aqueous solutions. International Journal of Nano Dimension,

7(2), 109-120.

Sajid, M., & Basheer, C. (2016). Stir-bar supported micro-solid-phase extraction for

the determination of polychlorinated biphenyl congeners in serum samples.

Journal of Chromatography A, 1455, 37-44.

Sajid, M., Basheer, C., Alsharaa, A., Narasimhan, K., Buhmeida, A., Al Qahtani, M.,

& Al-Ahwal, M. S. (2016). Development of natural sorbent based micro-

solid-phase extraction for determination of phthalate esters in milk samples.

Analytica Chimica Acta, 924, 35-44.

Sajid, M., Basheer, C., & Mansha, M. (2016). Membrane protected micro-solid-

phase extraction of organochlorine pesticides in milk samples using zinc

oxide incorporated carbon foam as sorbent. Journal of Chromatography A,

1475, 110-115.

63

Salisaeng, P., Arnnok, P., Patdhanagul, N., & Burakham, R. (2016). Vortex-assisted

dispersive micro-solid phase extraction using ctab-modified zeolite nay

sorbent coupled with hplc for the determination of carbamate insecticides.

Journal of Agricultural and Food Chemistry, 64(10), 2145-2152.

Samiey, B., Cheng, C.-H., & Wu, J. (2014). Organic-inorganic hybrid polymers as

adsorbents for removal of heavy metal ions from solutions: A review.

Materials, 7(2), 673.

Sanagi, M.M., Loh, S.H., Wan Ibrahim, W.A., Pourmand, N., Salisu, A., & Ali, I.

(2016). Agarose- and alginate-based biopolymers for sample preparation:

Excellent green extraction tools for this century. Journal of Separation

Science, 00, 1-8.

Sanchez, C., Julian, B., Belleville, P., & Popall, M. (2005). Applications of hybrid

organic-inorganic nanocomposites. Journal of Materials Chemistry, 15,

3559-3592.

Shah, I., Adnan, R., Wan Ngah, W. S., & Mohamed, N. (2015). Iron impregnated

activated carbon as an efficient adsorbent for the removal of methylene blue:

regeneration and kinetics studies. PLOS ONE, 10(4), e0122603.

Shah, I., Adnan, R., Wan Ngah, W. S., Mohamed, N., & Taufiq-Yap, Y. H. (2014).

A new insight to the physical interpretation of activated carbon and iron

doped carbon material: Sorption affinity towards organic dye. Bioresource

Technology, 160, 52-56.

Shah, M. P., Patel, K. A., Nair, S. S., & Darji, A. M. (2013). Microbial

decolorization of remazol brilliant orange 3r, remazol black b &amp; remazol

brilliant violet dyes in a sequential anaerobic-aerobic system. International

Journal of Environmental Bioremediation & Biodegradation, 1(1), 6-13.

64

Shankar, P. (2008). Coconut shell based activated carbon with no green house gas

emission. Water Conditioning & Purification, Singapore. Filtrex

Technologies, 1-4.

Sharma, P., Kaur, H., Sharma, M., & Sahore, V. (2011). A review on applicability of

naturally available adsorbents for the removal of hazardous dyes from

aqueous waste. Environmental Monitoring and Assessment, 183, 151-195.

Souza, V., & Quadri, M. (2013). Organic-inorganic hybrid membranes in separation

processes: a 10-year review. Brazilian Journal of Chemical Engineering,

30(4), 683-700.

Srinivasan, R. (2011). Advances in application of natural clay and its composites in

removal of biological, organic, and inorganic contaminants from drinking

water. Advances in Materials Science and Engineering, 2011.

Tran, V.S., Ngo, H.H., Guo, W.S., Zhang, J., Liang, S., Ton-That, C., & Zhang, X.

B. (2015). Typical low cost biosorbents for adsorptive removal of specific

organic pollutants from water. Bioresource. Technology, 182, 353-363.

Trasande, L., & Liu, Y.H. (2011). Reducing the staggering costs of environmental

disease in children, estimated at $76.6 billion in 2008. Health Affair, 30, 863-

870.

Turcu, R., Bica, D., Vekas, L., Aldea, N., Macovei, D., Nan, A., & Pop, C. (2006).

Synthesis and characterization of nanostructured polypyrrole-magnetic

particles hybrid material. Romanian Reports in Physics, 58(3), 359.

Xiong, X., Yang, Z., Huang, Y., Jiang, L., Chen, Y., Shen, Y., & Chen, B. (2013).

Organic–inorganic hybrid fluorous monolithic capillary column for selective

solid‐phase microextraction of perfluorinated persistent organic pollutants.

Journal of Separation Science, 36(5), 923-931.

65

Yahaya, N., Mitome, T., Nishiyama, N., Sanagi, M. M., Wan Ibrahim, W. A., & Nur,

H. (2013). Rapid dispersive micro-solid phase extraction using mesoporous

carbon COU-2 in the analysis of cloxacillin in water. Journal of

Pharmaceutical Innovation, 8(4), 240-246.

Yang, Y.Q., & Han, S. Y. (2005). Nanoclay and modified nanoclay as sorbents for

anionic, cationic and nonionic dyes. Textile Research Journal, 75, 622-627.

Zhang, X., Gui, Y., & Dong, X. (2016). Preparation and application of TiO2

Nanotube array gas sensor for SF6-insulated equipment detection: A review.

Nanoscale Research Letter, 11(1), 302.

Zhao, Y. G., Chen, X. H., Pan, S. D., Zhu, H., Shen, H. Y., & Jin, M. C. (2013).

Simultaneous analysis of eight phenolic environmental estrogens in blood

using dispersive micro-solid-phase extraction combined with ultra fast liquid

chromatography–tandem mass spectrometry. Talanta, 115, 787-797.

Zhou, Q., & Fang, Z. (2015). Graphene-modified TiO2 nanotube arrays as an

adsorbent in micro-solid phase extraction for determination of carbamate

pesticides in water samples. Analytica Chimica Acta, 869, 43-49.

Zhou, Q., Fang, Z., Li, J., & Wang, M. (2015). Applications of TiO2 nanotube arrays

in environmental and energy fields: A review. Microporous and Mesoporous

Materials, 202, 22-35.